Nickel(0)‐Catalyzed Hydroalkenylation of Imines with Styrene and Its Derivatives

• Published in: Angewandte Chemie International Edition Vol. 57; no. 13; pp. 3396 - 3400
• Main Authors: Xiao, Li‐Jun, Zhao, Chao‐Yue, Cheng, Lei, Feng, Bo‐Ya, Feng, Wei‐Min, Xie, Jian‐Hua, Xu, Xiu‐Fang, Zhou, Qi‐Lin
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 19.03.2018; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Aliphatic compounds; Alkenes; allylic compounds; Amines; Chemistry; Chemistry, Multidisciplinary; Derivatives; Imines; Mathematical analysis; Nickel; Physical Sciences; reaction mechanisms; Reagents; Science & Technology; Styrene; nickel; ALDIMINES; VINYLATION; reaction mechanisms; imines; ALDEHYDES; alkenes; ALKYNES; BOND-FORMING HYDROGENATION; ALLYLIC AMINES; RH; allylic compounds; OXIDATIVE CYCLIZATION; SIMPLE ALKENES; ASYMMETRIC HYDROVINYLATION
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201713333

A nickel(0)‐catalyzed hydroalkenylation of imines with styrene and its derivatives is described. A wide range of aromatic and aliphatic imines directly coupled with styrene and its derivatives, thus providing various synthetically useful allylic amines with up to 95 % yield. The reaction offers a new atom‐ and step‐economical approach to allylic amines by using alkenes instead of alkenyl‐metallic reagents. Experiments and DFT calculations showed that TsNH2 promotes the proton transfer from the coordinated olefin to the imine, accompanied by a new C−C bond formation. In the nick of time: A nickel(0)‐catalyzed hydroalkenylation of imines with styrene and its derivatives is reported. The reaction offers a new atom‐ and step‐economical approach to allylic amines by using alkenes instead of alkenylmetal reagents. PG=protecting group, Ts=4‐toluenesulfonyl.